Azo-dyestuffs and process of making same



Patented July 12, 1932 one JOSEPH GYR AND OTTO KAISER, OF BASEL, SYVITZERIIAND, ASSIGNORS TO THE FIRM SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND AZO-DYESTUFFS AND PROCESS OF MAKING- SAME No Drawing. Application filed October 16, 1928, Serial No. 312,328, and in Switzerland October 22, 1927.

The present invention relates to the manufacture of new direct dyeing azo-dyestufis, It comprises the process of making these dyestufis, the dyestufis themselves, and the material that has been dyed with the new products. V

In the U. S. specifications Nos. 1,625,530, 1,625,531, 1,625,532, 1,625,533 and 1,667,312 intermediate products and azo-dyestufis are described which are characterized by the presence of a cyanuric ring. This fundamental invention has also been described in a number of foreign specifications, thus inter alia in British specifications 221 841 and 209,723, French specifications 572,715 and 576,725, and German specification 436,17 9. The dyestuffs are mostly cotton dyestuffs which are distinguished for their purity of tint, their dyeing capacity and the fastness to light of their dyeings.

According to the present invention new direct dyeing azo-dyestufis, which may be characterized by dyeing properties essentially better than those of otherwise comparable dye- Y stufis, are made by introducing the thiazole ring into dyestuffs of the kind described in the said specifications, the introduction occurring either into the diazo component or into the coupling component or into both components,

These new direct dyeing dyestuffs may be made by condensing a cyanuric halide with such components as contain at least one hydrogen atom which can react with a cyanuric halide, at least one of such compounds containing at. least one group adapted for azodyestuif formation, or a residue capable of transformation into such a group, or an azochromophor, and at least one of such compounds containing at least one thiazole ring. The products thus obtained, particularly when they contain no azo-chromophor, may be converted into azo-dyestufi's, if necessary after transferring the aforesaid residue into a group adapted for azo-dyestuff formation, either by diazotization and coupling with a coupling component, or by coupling with any desired diam-compound. Such dyestuffs may also be obtained by coupling a diazobody with a coupling compound if these com- The new dyestuffs form powders more or less intensively colored, dissolving in water to solutions of all colors of the spectrum and ofthose which are obtained by combination of the said colors, and dyeing the textile fibre from cellulose or regenerated cellulose similar tints. l V The invention permits the production of a: very large number of intermediate products and dyest-ufis. therefore, only some single members of. the principal types of the new products can be adduced for the purpose of indicating the scope of the invention, and it is obvious that In the following examples,

the same embraces everything which results so by interpolation and combination of the products described both among themselves and with the products of the aforesaid specifications.

In the examples the parts are by weight Example 1 A fine suspension of 18.5 parts of cyanuric chloride in ice water is mixed with a neutral solution of 31.9 parts of 1: S-aminonaphthOI- 3 6-disulfonic acid and the mixture is stirred for 11 hours at 0 C. During this time there is run in gradually a solution of 5.3 parts of sodium carbonate. added a neutral solution of 32 parts of dehydrothiotoluidinesulfonic acid, the temperature is raised to 40 C. and in the course of 1% hours a solution of 5.3 parts of sodium carbonate is allowed to flow in. From the ma There is then 5 when filtered and dried it is a pale yellow powder.

.The formula of the new intermediate product is very probably the following:

H-N O H NHz- By adding to the above described aqueous solution of the secondary condensation prodnot 9.3 parts of aniline and'heating for 1 hours at 80 C, there is formed the tertiary condensation product from 1 molecule cyanuric chloride, 1 molecule 1: S-aminonaphthol- 3: 6-disulfonicacid, 1 molecule dehydrothiotoluidinesulfonic acid and 1 molecule aniline; this may be salted out and isolated. It forms a pale yellow powder. I p

The 7 same product is obtained when the three components are caused to act on the cyanuric chloride in another order.

Both the secondaryand tertiary condensation products are nearly colorless in alkaline solution but on acidification become yellow. They show pronounced substantive character in that they are adsorbed by cotton without development of color in a feebly alkaline bath of Glaubers salt and can be developed, after rinsing, with various diazo-solutions to produce powerful dyeings.

Ewample 2 18.5 parts of cyanuric chloride finely suspended in icewater are mixed with a neutral solution of 18.8 parts of l 4c-phenylenediamine-3-sulfonic acid and the mixture is stirred at O5 C. In the course of 1 hours a solution of 5.3 parts of sodium carbonate are allowed to flow in. To the slightly slimey condensation mass there is then added a neutral solution of 32 parts of dehydrothiotoluidinesulfonic acid and the whole is heated to 40 C. Within one hour a further solution of 5.3 parts of sodium carbonate is run in, the temperature is kept at 40 C. for some time and the secondary condensation product. formed from 1 molecule cyanuric chloride, 1 molecule 1: t-phenylenediaminesulfonic acid and 1 molecule dehydrothiotoluidinesulfonic acid, corresponding very probably with the formula is caused to separate by saltingoutor by acidification. In the form of its sodium salt it is a nearly colorless powder; the free acid is yellow. Theproduct has a substantive character; it is adsorbed colorless by cotton in a feebly alkaline bath of Glaubers salt and after the fibre has been rinsed the. adsorbed substance may be developed to strong dyeings by diazotizing and coupling with the most various azo-components.

This secondary condensation product may further be condensed to a tertiary product, for instance by adding to the solution described above 9.3 parts of aniline and heating for about 2 hours at (3., whereby there ,ilar to those of the above secondary product,

and corresponds very probably with the formula ELM

N Y N s 1 CH1 03H The product can also be obtained by causing the components to act on the cyanuric chloride in another order, for instance the dehydrothiotoluidinesulfonic acid may be condensed in the first place.

Isomeric products having similar properties are obtained by substituting its sulfonic acids for the aniline and monoacetyl-paraphenylenediamine or para-nitraniline for the para-phenylenediamine sulfonic acid and then saponifying or reducing the tertiary condensation product so formed.

Ewample 3 parts of sodium carbonate is allowed to flow in and the temperature is then slowly raised to C. where it is kept for 2 hours. The whole is then made neutral to congo With a solution of 3 parts of sodium carbonate and a neutral solution of 32 parts of dehydrothiotoluidinesulfonic acid added. The temperature is now quickly raised to 80 C'. and in the course of it there is again allowed to flow into the mass a solution of 2.5 parts of sodium carbonate. After a further hour the formed condensation product is saponified by adding to'every 1000 parts by volume of the solution 180 parts by weight of a caustic soda solution of 30 per cent. strength and keeping the temperature at 7 580 C. for one hour. The solution is then neutralized with hydrochloric acid and the dyestuif is precipitated by addi tion of common salt. The product thus obtained is the tertiary condensation product from 1 molecule cyanuric chloride, 2 molecules of the monoazo-dyestuff from diazotized 1: 8-aminonaphthal-3 6-disulfonic acid and 1-Inethyl-3aminophenyl-l-methylether, and 1 molecule dehydrothiotoluidinesulfonic acid. It corresponds very probably with the formula OOH: OCHa l I O prtjig CHa SOaH

J tints which are fast to light.

Ewample 4 9.3 parts of aniline are diazotized and introduced into the solution, alkaline with sodium carbonate, of 75 parts of the secondary condensation product from 1 molecule cyanuric chloride, 1 molecule 1:8-aminonaphthol-3z6-disulfonic acid and 1 molecule dehydrothiotoluidinesulfonic acid. The dyestufl formed is precipitated by adding common salt, and corresponds very probably with the formula Hat l O H HOsS SO5H It dyes cotton pure rose tints.

The same dyeing can be produced on the fibre by impregnating or dyeing the fibre with the secondary condensation product and then developing with diazobenzene.

E'azample 5 The diazo-compound from 13.7 parts of 2-aminobenzoic acid is allowed to flow into a solution, alkaline with sodium carbonate, of 75 parts of the secondary condensation product from 1 molecule cyanuric chloride, 1 molecule 1 8-aminonaphthol-8 6-disulfonic acid and 1 molecule dehydrothiotoluidinesulfonic acid. The dyestufii' is precipitated and its separation may be completed by salting out. It corresponds very probably with the formula N\ /N a/ MHO/ I i fr crn T E coon M3 noss- S0311 OHa SOaH

and dyes cotton clear rose tints, which become a light red-dish violet fast to light by treatment with copper on the fibre. The same dyeing is obtained with the dyestuff which has been previously treated with an agent yielding copper to convert it into a complex copper compound and has been then dyed on cotton.

If in the foregoing example there are sul stituted for the couplingcomponent727 parts of the tertiary condensation product from 1 molecule cyanuric chloride, 1 molecule 2: 5- aminonaphthol-7-sulfonic acid, 1 molecule dehydrothiotoluidinesulfonic acid and 1 molecule aniline, there is obtained a dyestufi' which dies cotton clear orange tints. By treatment with copper on the fibre the tine becomes reddish-brown fast to light; this is also obtained when the dyestuti is previously converted in substance into the complex copper salt and then dyed on the cotton.

Example 6 N LII s Woiu y a r Hogs -s0311 g soar! and dyes cotton red-violet tints. By treatment with copper on the fibre or by dyeing in presence of a copper salt a reddish-violet fast to light is obtained. The dyestufi may also be converted directly into a complex copper compound, for instance, by treatment with copper sulfate; the same tints on cotton are produced by this compound.

This copper compound can also be made in the following manner :-The diazo-compound from 18.8 parts of l-oxy-Q-aminobenzene-lsulfamide is coupled with a solution of 31.9 parts of 1: 8-aminonaphthol-3 6-disulfonic acid with addition of milk of lime, the dyestuff is separated, then dissolved and converted into the complex copper salt by boiling it with a co er salt. The copper compound corresponding with 51.8 parts of dyestuff free from copper is dissolved, in the form of its neutral ammonium salt, in 1200 c. c. of hot water and the solution is mixed with a suspension of 18.5 parts of cyanuric chloride in water and much ice and the Whole stirred at 0 C. for 2 hours. To the violet solution there are then added 32 parts of dehydrothiotoluidinesulfonic acid, the tempera-- ture is raised gradually to 50-60 C. and in the course of one hour a solution of 10.6 parts of sodium carbonate is run in. The dyestutf separates and is isolated by filtration.v It dyes cotton in the same red-violet tints as are produced by the copper compound described above.

The corresponding 'dyestutf containing chromium dyes cotton violet.

Example '7 62 parts of the secondary condensation product from 1 molecule cyanuric chloride, 1 molecule 1 4 phenylenediamine-3-sulfonic acid and 1 molecule dehydrothiotoluidinesulfonic acid described in Example 2, are diazotized at 1015 C. and coupled with a soluand dyes cotton clear greenish yellow tints.

Example 8 Into a neutral solution of 50 parts of the secondary condensation product from 1 molecule cyanuric chloride, 1 molecule 2: 5-aminonaphthol-7-sulfonicacid and 1 moleculemono-acetyl-l -phenylenediamine, and stufi yielding somewhat yellower dyeings on parts of sodium acetate, there is caused to cotton. A

flow at 45 C. a diazo-compound from 32 By saponifying the dyestufl', for example, parts of the dehydrothiotoluidine-monosulby heating it with dilute caustic soda solufonic acid obtainable by baking dehydrothiotion, the acetyl group is eliminated; the dyetoluidine sulfate. When coupling is comstufi? produced can be diazotized on the fibre plete the dyestufi? is salted out and isolated.. and developed by ,B-naphthol.

It corresponds very probably with the for- The number of examples could be multimula plied as desired; it suffices, however, to refer i HOaS N-C o-N- N-H N O N=N @I I N 1 1 =d-orn HaC- 7 and dyes cotton scarlet-red tints fast to light. to the numerous combinations indicated in If for the dehydrothiotoluidine sulfonic the specifications referred to in the introducacid prescribed above are substituted 40 parts tion to this specification. V

of the dehydrothiotoluidine-disulfonic acid In the following tables the constitution obtainable by further sulfonation of the and dyeing properties of a further small above-named dehydrothiotoluidine-monosulnumber of dyestuffs obtainable according to fonicacid, there is produced a similar dyethe invention are given.

Table A Coupling component by condensation of cyanurie halide with- Diazoconiponent fron1 Dyeing on cotton 1. Component 2. Component 3. Component (1) Aniline l-amino 8 oxynaph Dehydrothiotoluidine- Rose.

" thalene-BzG-disulfonic sulfonic acid.

aci (2) Orthotoluidine do V Bluish rose. (3) Paratoluidine- -do D0. (4) Meta-xyhdine do 1 D0. (5) Para-xylidine do Do. (6) 2z5-dichloraniline d0 Rose. (7) 4-aminoacet-anilide. do Violet. (8) 3-aminobenzoie acid do Rose. (9) 4-amino-benz0ic acid do. Do. (10) 2-aminobenzoic acidomethy1ester -do Do. (11) 3-aminobenzenesulfamide do D0,. (12) 2-anisidine do Bluish rose. (13) 4-ch1oro-2-aminodiphenylether l-amino 8 oxynaph- Do.

thalene 3 6 disulfonie acid.

(14) 2-amino-4-acetamino-4-methy1- do do Red violet.

dipheuyl-sulfone. (15) 4-methyl-4-aminodiphenylamine- 1 amino 8 oxynaph d Blue.

z-sulionic acid. thalene 3 z 6 disul ionic acid.

(16) 4-chloro-2 aminophenol; do' d Blue violet (1). (1 7) Monoformyl-l': 8-phenylen'ediam- (S(a210n1fied)redred 1119. (18) l-naphthylamine Bluish violet.

Reddish violet. r Violet.

(19) 2-naphthyla1nine (20) Dehydrothiotoluidine o sulfonic acid. (21) Dehydrothiotoluidine D0. (22) Aminoazo-benzene Do.- (23) Aniline 2: 5 disulfonic acid azo- Greenishblue.

1 -gmethyl 3 aminophenyl 4 -Inethy1- et er. (24) Monoacetyl 1:3 -pheny1 enediam- Do.

ine-el-sulfonic acid azo-l-inethyl 3 amino-phenyl4-methylether. I (25) 4-nitrani1ine-2'su1fonic-acid-az0-l- D0.

methyl-3-aInino-phenyl-4-rnethylether. (26) 1 amino-S-oxynaphthalene-Zi, 6 dil-amino-S-oxynaphtha- (io' Do.

sulfonioacid azo-l-methyl-3-an1inolene 3,6 disulfonic benzene 4-methylether. acid. 7) Do l-alnino-8-oxynaphtha- -do. D0. 1

lene-4,6disu1fonic acid. (28) 1 amino -8-oxynaphtha1ene 3,6- l-amino-S-oxynaphthado Do.

disulionie-acid azo-l-naphthylamine. leng 3,6 disulfonic 1 (29) 4-au1ino-pheny1oxaminie acid az0-1- Do.

methyl-3amino-phenyl-4-methylether. (30) Benzidine Blue.

(s1) Aniline..- Rose (32) Z-anisidine Bluis h rose.

Table AContinued Diazocomponent from- Coupling component by condensation of cyanuric halide with 1 Dyeing on cotton 1. Component 2. Component 3. Component 70 (33) 4-nitraniline-sulionic acid azo-l- 1 amino-8:0xynaphtha- Dehydrothiotoluidine. Greenish blue,

- methyl 3 -arninophenyl 4 -methyl 18118-326d15111f0fli0 acid.

- ether.

. (34) l-annno-8-oxynaphtha1ene-3,6 dido ..d0 Do.

sulfouic-acid' azo-l-methyl-li-aminophenyl--methylether. I 5

(35) Aniline Dehydrothioxylidine- Rose,

sulfonic acid. (36) 4-to1uidine d0 n Bluish rose. (37) 2-anisidine... do Dehydrothiotolurdlne- Aniline Do,

- sullonic acid.

(38) Dehydrothioxylidine do do..- do Violet. N

(39) 4 nitraniline-2-sulfonic-acld-azo-ldo do do Greenis h blue. I .80

methyl-3-aminophenyl-4-methylether.

(40) Aminoazobenzene do .d0 'do Violet.

(41) 1-amino-8-oxynaphthalene-3,6-d1Suld0 do do Greenish blue,

ionic acid azo 1 methyl 3 aminophenyl-4-methy1-ether.

(42) l-amino-S-oxynaphthalene-3,6-d1suldo dn dn D fonic-acid-azo-l-naphthylamine.

(44 Aniline PllmllllDG-SHHODIO ae1d Yellowish rose.

(45) 2-anisidine do ed,

(46) 4 nitraniline 2 sulfonicacid Greenish blue.

azo 1 methyl 3 amino phenyl 4 methylether. (4'7) 1 Amino 8 ox'ynaphth'alene 3.6- do do don Do. disulfoni'c acid azo 1 methyl 3 Vaminophenyl-Qmethylether.

(4s) Aniline 1 n Dehydrothiotoluidme- D ehydrothiotolui- Rose. 90

v sulionic acid. dinesulionic acid.

(49) 2-anisidine Bluishrose.

(50) 4 nitraniline ulfo cid azo Greenish blu 1 methyl 3 aminophenyli-meth ylether.

(51) 1 amino 8 oxynaphthalene 3:6- .do Do.

disulfonic acid azo 1 methyl 3- amino-pheny1-4-methylether y 7 (52) Aniline -2:5 -disullonicac1 d -&Z0 1- d0 .do do Grey blue.

naphthylamine 7 sulfonic acidazo-l-naphthylamine.

(53) 4' methyl 4 amlnodlphenylv d0 do 4-chloro-lz3-diamino- Blue.

emine-2-s11ll0nic acid. benzene.

(54). 1 amino 8 oxynaphthalene 3:6- d0 do "do Blue green (3).

disulfonicacid azo 1 methyl 3- r l aminophenylA-methylether.

(55) 4 amin'ophenyl-oxaminic acrddo do dn Blue blaclr. 0

azo 1 methyl 3 aminophenyl 4 methylether.

(56) 3-aminobenzoicaciduu; do rln 4' ammo-4-hydroxy- Yellowish red.

' azobenzene- 3 1 carboxylic acid.

(57) 4-aminophenyl-oxaminic acld-azodo n .Jlo Greenish grey.

1 methyl 3 aminopheny1-4 -methylether. 105

(58) Monoacetyl 1:3-iphenylene-d1amdo do do Greenish blu ine 4 -'sulionic acid-azo-l methyl-B- aminophenylA-methylether.

(59) 1 amino 8 oxynaphthalene-fizfi- -d0 do do Bluish green.

disulfonic acid-azo-l methyl-B-ammophenyli-methylether; d V d d B h d (60) 2-aminopheuol-4-suliamlde 'Brownish violetfl).

lene-7-sulionic acid.

(63) 2-a1n1no-benzoic-acid Orange.

(64) 2-amiI10phenO1-4Snlfamirln Bordeaux ruby (1).

(65) 4-ch1oro-2-aminophenol;; .5. Red violet (l).

(66) Dehgdrothio toluidinedisuli'cnlc Scarlet.

aci

(67) Benzidine Violet. 115

(68) Secondary condensation product Bluish red borfrom 1 mol. cyanuric chloride, 1 mol. deaux (1). 1:4-phenylenediamiue sulfonic acid and 1 mol. 5-aminoQ-oxybenzene-can A boxylic acid.

(69) Aminoazc-benzene-sulfonic acid Bluish red.

(70) 2-amino-benzoic acid Orange brown (1).

(71) 2-amino-phenol-4-su1famide. Brownish violet 190 bordeaux (1).

(72) Dehydrothio-toluidinesulfonic acid. Scarlet.

(73) l1)chydrothio-toluidinedisulfonic Do..

(74) 1 amino 8 oxynaphthalene 3:6- Blue.

drsulfonic acid-azo-l-methyl-3-aminophenyl- 4-methylether.

(75) Amhne 2-amino-8-oxynaphthado Scarlet.

(76) 2-am1n0benzo1c acid do rln Scarlet bordeaux diamine. 1:3 phenylenediamme- 4-sdullonic acid.

4-amino-acetanilide Table A-Continued Diazocomponent from- Dyeing on cotton 1. Component 2. Component 3. Component (81) Aniline l-amino-8-oxynaphthal-amino-B-oxynaphtha- Dehydrothio tolui- Aniline lene 3:6 disullonic lene 3:6 disulfonic dine. Rose. d acid. acid.

82 2-anisi ine (83) zfinisidile 21 do do do }Blu1sh rose.

2-an1inoenzoic aci iamino-begzoic acid. do r }Rose 84 minoazoenzene Amdnoazo-benzene. gfigg -.do do Deliydrothio tolui }Rose. (86) g do do dlggsunonic and }B11n'sh rose 2-anisi me (87) Z-amino-benzoic acid. 1

2-amino-benzoic acid do red V1019;

d do do }Bordeaux. do 2 amino oxynapthado }Yellowish red. 1ene-7-sulf0nic acid. I do do }Bluish red. (91) 2'an1ino-1: n1

2-ar n ino-1:4-dimethylbenzene (92) 323$: I do 2-amino-8-oxy naplltha- Do. (93) fg y g 1ene-6-sulfon1c-ac1d. }Rose 0 in me 4-amino-4-hydro cyazo- Greenish-yellow.

sulfonic acid. benlzene 3 carboxylic acl (95). do 4-amino-4-hydroxy- Do.

azo-benzene-3-carboxylic acid.

Table B Diazo-components by condensation of cyanuric halide with:

1. Component 2. Component 3. Component Coupling component Dyeing on cotton (96) 1:4- phenylenediarnine-2-sulfonic acid.

Dehydrothiotoluidinesulfonic acid.

(l05) Do (106) .D0 do (107) Do .do

(s) D do (109).--.D0 do (110) 4-ch1oro-1:3-phenyldo enediamine.

(111) .Do do -ohloro-lzS-phenyl- Dehydrothiotoluidinen2) enediarnine. sulfonic acid.

( 4-chloro-1z3-pheny1- Dehydrothrotoluidineenediamine. sulionic acid. (113) 1:4 phenylenediam- Dehydrothiotoluidlna ineZ-sulfonic acid.

(l14) Do sulionic acid.

1:3-pheny1enediamine-4- sulfonic acid.

do Aniline Dehydrothiotoluidine-sulfonic acid.

Resorcin 1 z3-phenylenedian1ine Phenylmethyl-pyrazolone 2-naphthol-6-sulfonic acid 2-amino-8-oxynaphthalene-G-s acid (acid coupled).

2-amino-5-oxynap11thalene-7-sulfonic acid (alkaline coupled).

2-phenylarnino-5-oxynaphthalene-7- sulfonic acid.

3-aminophenyl-5-oxy-l:2-naphthimidazole-7-sull'onic acid.

3-arninopheny1-5-oxy-1:2-naphththiazol-7-sulfonic acid.

1-acctylamino-8-oxynaphthalene-3:6-

disulfonic acid.

Secondary condensation product from 1 mol. cyauuric chloride. 1 mol. l-arnino-8-oxynaphthalene-3 :6- disulfonic acid and 1 mol. dehydrothiotoluidinesulionic acid.

Secondary condensation product from 1 mol. cyanuric chloride, 1 mol. 2-amino-5-oxynaphtha1ene-7- sulfonic acid and 1 mol. 1:4-phenylene-diamine-Z-sulfonio acid.

Secondary condensation product from 1 mol. cyanuric chloride, 1 mol. 2-amino'5-oxynaphtha1ene-7- sulfonic acid and 1 mol. 1:3-pl1eny1- enediarnine-l-sulfonic acid.

Secondary condensation product from 1 mol. cyanuric chloride and 2 mols. l amino-8'oxynapl1tha1ene- 3:6 disulfonic acid.

2-amino-1z4-diarnethylbenzene, further diazotized and coupled with 2-phenyl-a1nino-5-oxynaphthalene- 7-sullonic acid.

2-amino-lz l-diarnethylbenzene, further diazotized and coupled With 2- arncilno-5-oxynaphthalene-7-sulfonic aci 2 mols. Z-amino-S-oxynapthalone-6- sulfonic acid (acid coupled).

2 mols. acetoacetic anilide 3-arninophenyl-5-oxy-lzit-naphththiazole-7-sulfonicacid.

Yellowish-orange.

Y e l l o w b r o w n brown (4) 0 range.

Greenish-yellow.

Bluish-red.

Red.

Red.

Reddish violet.

Bluish red bordeaux (2).

Red-violet.

Violet.

Red red (2).

Rose.

Greenish yellow. Red red (2).

The formula of the dyestufi (No; 23) is very probably H 7 The formula of the dyestuif (No. 38) is very probably SOaH The formula of the dyestuff (N0. 52) is very SOaH *If dy'estuff No. 26, in accordance with the data of Example 3, has been made from the para-toluenesulfonic acid ester of 1:8-aminonaphtho1-8: G-disulfonic acid, the

5 last chlorine atom of the cyanurlc ring is then replaced by an OH-group.

The formula of the dyestufi (No. 56) is very probably H30 l 1% 111' l p 00011 00011 no I!IH HO: 803E The formula of the dyestufi (No. 68) is very probably The formula of the dyestuif (No. 96) is very probably HoH-N-- N-H, OH 4.5 M

no. 0811 B038 SOBH o1 e r a 01-- N-ii (LN-O Iii 1i s v i The formula of dyestufi' (No. 113) is very probably H035 i o1 N "x NO 1 N W") (LN N N N e M A it A v 0,11 H; V H 55 :11

r 6 p N a 00011 HOaS I -iK b-NOQ @som BOON- (ii-N N=NI 7 H M s H3 The numbers which follow some of the colors diazotization components of the benzene, or of the dyeings in the above table have the naphthalene series to react in ortho-position following significance p 7 to the OH-group on such coupling compo- (1) After-treatment with copper or dye'-' nents, of the general formula Y Y ing in the form of copper salt. I V

(2) Diazotizing on the fibre and developing with B-naphthol.

(3) Diazotizing on the fibre and developing with phenylmethylpyrazolone.

(4) Developing on the fibre with 4=-I1it10 diazobenzene.

It is clear that other aminoand oxy-thiazoles not named in the foregoing tables or examples, may be used. Such are described in literature, for example in British specifications Nos. 406 of 1894, and 3026 of 18.94 and in German specifications Nos. 7 9,093, 81,711, 83,089, 97,285, 98,813,277395.

What we claim is g V 1. A process for the manufacture of new wherein a: stands for halogen or a residue which can replace halogen and wherein the naphthalene nucleus and the benzothiazole complex each contains at least one sulfo group. p

4. A process for the manufacture of new direct dyeing v,azo-d'yestuffs containing at direct dyeing azo-dyestufli's containing at least one thiazole ring and at least one cyaleast one thiazole ring and at least one cyanuricring, consisting in causing diazotized nuric ring, consisting in causing diazotized diazotizationcomponents of the benzene or diazotization components of the benzene or naphthalene series to react in ortho-position naphthalene series to react on coupling comto the OH-group on such coupling compoponents, these components being so selected nents of the general formula that at least one component contains at least wherein at stands for halogen or a residue one thiazole ring and at least one component. which can replace halogen, and wherein one 1 contains at least one cyanuric ring. of the ys stands for an H atom and the other 7 2. A process for the manufacture of new" for an SOQH group.

direct dyeing azo-dyestufis containing at 5. A process for the manufacture of new least one thiazole ring and at least one 'cyadirect" dyeing azo-dyestufi's containing at nuric rin consistin in causin diazotized least one thiazole rin v and at least one 0 ag7 g 2:: z: 110

diazotization components ofthe benzene or nuric ring, consisting in" causing diazotized naphthalene series to react on such coupling mononuclear cliazotization components of the components of the naphthaleneseries which benzene or naphthalene series to react in contain at least one thiazole ring and at least ortho-position to the OH-group on such cou one cyanuric ring. pling components of the general formula 3. A process for the manufacture of new stands forhalogen or a residue direct dyeing azo-dyestufi's containing at which can replace halogen, andwherein one least one thiazole ring and at least one cyaof the ys stands for an H atom and the other; a

nuric ring, consisting in causing diazotized yfor an SO H group. 7

6. A process for the manufacture of new direct dyeing azo-dyestufi's containing at least one thiazole ring and at least one cyanuric ring, consisting in causing diazotized diazotization components of the benzene or naphthalene series containing an azo-chromophor to react in ortho-position to the OH- group on such coupling components of the general formula ll wherein m stands for halogen or a residue which can replace halogen, and wherein one of the ys stands for an H atom and the other y for an SO H group. v

7 As new products the direct dyeing azodyestuifs deriving from diazotizing components of the benzene or naphthalene series characterized by the simultaneous presence in their molecule of at least one cyanuric ring and at least one thiazole ring, which products form powders more or less intensively colored, dissolving in water to solutions of all colors of the spectrum and of those which are obtained by combination of the said colors, and dyeing the textile fibre from cellulose similar tints.

8. As new products the direct dyeing azodyestuifs deriving from diazotizing components of the benzene or naphthalene series and from such coupling components which contain in their molecule simultaneously at least one cyanuric ring and at least one thiazole ring, which products form powders more or less intensively colored, dissolving in water to solutions of all colors of the spectrum and of those which are obtained by combination of the said colors, and dyeing the textile fibre from cellulose similar tints.

9. As new products the direct dyeing azodyestuffs deriving from diazotizing compo- SOzH nents of the benzene or naphthalene series and from such coupling components which contain in their molecule simultaneously one naphthalene nucleus, one cyanuric ring and one thiazole ring, which products form dark powders, dissolving in water to red, violet, blue or green solutions, and dyeing cotton similar tints.

10. As new products the direct dyeing azo- OHa dyestuffs of the general formula wherein R stands for the residue of any diazotization component of the benzene or naphthalene series, 0: stands for halogen or a residue which can replace halogen, and wherein one of the 'ys stands for an H atom and the other 3 for an SO H group, which products form dark powders, dissolving in water to red, violet, blue or green solutions, and dyeing cotton similar tints.

11. As new products the direct dyeing azodyestuffs of the general formula wherein R stands for the residue of such a V diazotization component of the benzene or naphthalene series which contains an azochromophor, w stands for halogen or a residue which can replace halogen, and wherein one of the ys stands for an H atom, and the other 3 for an S0 11 group, which products- JOSEPH GYB. OTTO KAISER. 

